Solvent and ion-pairing effects on the chlorine kinetic isotope effect of t-butyl chloride
The solvolysis of t-butyl chloride and 1-adamantyl chloride was measured in mixtures of aqueous 2,2,2-trifluoroethanols and in mixtures of aqueous ethanols. The KIEs for t-butyl chloride at 25/sup 0/C in 94% TFE/water, and 60% ethanol/water (solvent mixtures with similar polarity) were 1.0097 and 1.0104 respectively. Further investigations showed a KIE of 1.0104 in 50% ethanol/water and 1.0105 in 100% ethanol while the isotope effect in the fluorinated ethanols rose from 1.0094 in 99% TFE/water to 1.0101 in 70% ethanol/water. The KIE in all these solvents were shown to be directly proportional to the nucleophilicity of the solvent and indicates nucleophilic attack on an ion pair. The similar KIE of t-butyl chloride in the ethanol/water solvents was found to support the contention that solvent polarity exerts a minimal effect on the chlorine KIE.
- Research Organization:
- Wisconsin Univ., Madison (USA)
- OSTI ID:
- 6950144
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ALCOHOLS
ALKANES
BUTANE
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE 35
CHLORINE 37
CHLORINE ISOTOPES
DATA
DECOMPOSITION
ETHANOL
EXPERIMENTAL DATA
FLUORINATED ALIPHATIC HYDROCARBONS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
MEDIUM TEMPERATURE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXYGEN COMPOUNDS
SOLVENT PROPERTIES
SOLVOLYSIS
STABLE ISOTOPES
WATER